CN102317383A

CN102317383A - Co-curable, conductive surfacing films for lightning strike and electromagnetic interference shielding of thermoset composite materials

Info

Publication number: CN102317383A
Application number: CN2010800077408A
Authority: CN
Inventors: J·J·生; D·K·科利
Original assignee: Cytec Technology Corp
Current assignee: Cytec Technology Corp
Priority date: 2009-02-16
Filing date: 2010-02-09
Publication date: 2012-01-11
Anticipated expiration: 2030-02-09
Also published as: CN102317383B; KR101687043B1; TWI534837B; CN104194454B; US8178606B2; US20120219786A1; JP5770106B2; CN104194454A; AU2010213946A1; WO2010093598A3; KR20110129896A; EP2396375B1; US8357740B2; US8772391B2; CA2752503A1; TW201035994A; BRPI1008254A2; WO2010093598A2; AU2010213946B2; US20130101833A1

Abstract

Embodiments of the present disclosure present electrically conductive, thermosetting compositions for use in surfacing films and adhesives. The surfacing films possess enhanced electrical conductivity, comparable to metals, without the use of embedded metal screens or foils. Such surfacing films may be incorporated into composite structures (e.g., prepregs, tapes, and fabrics), for example, by co-curing, as an outermost surface layer. In particular, compositions formed using silver flakes as conductive fillers are found to exhibit very high electrical conductivity. For example, compositions including greater than 45 wt. % silver flake exhibit resistivities less than about 55 mO/sq. In this manner, the surfacing films as an outermost conductive layer may provide lighting strike protection (LSP) and electromagnetic interference (EMI) shielding when used in applications such as aircraft components.

Description

Be used for the thunderbolt of same with thermosetting compound material and the co-curing conductivity meter facial mask of electromagnetic interference shield

Technical field

Embodiment of the present invention relate to conductive polymer compositions, and are specifically related to the surface and the binder film that are formed by the thermoset polymer compositions that adds conductive additive.

Background technology

Polymer matrix composite structure (PMC) is used for aerospace applications just more and more.For example, in commercial aircraft the usage quantity of PMC up to about 50%.PMC combines to be encapsulated in the selectivity directional fiber in the matrix material on every side.These composite structures present the working temperature window of favorable mechanical character (for example intensity, stiffness, toughness) and broadness and are easy to make with regard to its weight, this makes it be very suitable for aerospace applications.

Surface film, for example epoxy resin basement membrane are added in the polymer composites so that the matrix material with the required surface quality of aerospace applications to be provided usually.For example, can reduce labour, time and cost that matrix material is made simultaneously with surface film and prepreg co-curing so that the void-free basically surface that can protect down surface composite material to be provided.

Yet, because based on the insulating property of the surface film of epoxy resin, it is to presenting the resistibility of non-constant such as electromagnetic energy (EME) incidents such as thunderbolt (LS), Electrostatic Discharge and electromagnetic interference (EMI)s.The high relatively resistivity that epoxy resin appeared has suppressed the thunderbolt energy and has fully dissipated, and causes the perforate surface and the layering of following composite structure.In addition, the electric charge that is produced on the composite material surface can keep the long period section, makes the risk of ESD in the low relative humidity environment (it can damage electronic system) reach the risk raising that in the vapour space of fuel container, produces spark.In addition, can suppress the charged particle carrier migration based on the poor conductivity of the surface film of epoxy resin, this possibly slacken composite structure EMI is provided the ability of shielding.

For thunderbolt is minimized the influence of composite structure, used different modes to strengthen the electroconductibility of composite structure, so that protect for the composite part on the aircraft provides LS/ESD/EMI.The instance of these class methods comprises entity or sectional lightning rod, the metal through electric arc spraying or flame plating, knit wire reticulattion, entity paper tinsel/expansion paper tinsel/perforated foil, metal coat cloth, the high electro-conductive fiber of the wire cloth that interweaves (IWWF) and the electric conduction paint that is loaded with metal.In more another instance, expanded metal net (for example copper, aluminium reticulattion) is embedded in the surface film that attaches on the composite material surface, so that the energy that is caused by thunderbolt that dissipates resists this type of incident.

Yet the surface film system that unfriendly, has a buried metal net (for example copper or aluminium have the spun glass sealing coat) has significantly increased the gross weight of aircraft.In addition, with can significantly increasing material and the labour costs of making composite part in these surface film System integration to matrix materials.In addition; The mode of uniform conductive property interconnects to reach basically across many surface film possibly to be difficult to make these surface film; Cause electroconductibility discontinuous thus, electroconductibility is discontinuous possibly to cause the possibility increase and/or the EMI shielding that are damaged during LS or the ESD impaired.Particularly, wire netting further suffer burn into and matrix thermal expansion mismatch (this causes hallrcuts) and with matrix combine impairedly, its each LS/ESD/EMI that all can further weaken surface film and provided protects.

Summary of the invention

In one embodiment, a kind of conductivity meter facial mask is provided.This surface film comprises:

Thermoset polymer compositions, it comprises:

At least a thermosetting resin; And

At least a conductive additive, it comprises based on the gross weight of the compsn silver-colored thin slice greater than about 35 weight %;

Wherein the resistivity of surface film less than about 500 milliohms/square.

In another embodiment, a kind of conductivity meter facial mask is provided.This surface film comprises:

Thermoset polymer compositions, it comprises:

At least a thermosetting resin; And

The graphitized carbon black of about 2-8 weight %;

Wherein the resistivity of surface film is less than about 50 ohm-sq.

In yet another embodiment, a kind of matrix material that comprises this surface film is provided.

In another embodiment, a kind of electrically conductive composition is provided.Said composition comprises:

One or more thermosetting resins of about 10-60 weight %;

One or more solidifying agent of about 0.5-30 weight %; And

One or more conductive additives of about 2-70 weight %;

Wherein this concentration gross weight of being based on compsn is measured; And

Wherein the concentration of conductive additive is through selecting, so that this electrically conductive composition appears between about 1 * 10 ^-6Ohm-sq to 1 * 10 ⁸Resistivity between the ohm-sq.

In one embodiment, a kind of surface film that comprises said composition is provided.In another embodiment, a kind of matrix material that comprises this surface film is provided.In yet another embodiment, a kind of electrically conductive adhesive film that comprises said composition is provided.

In another embodiment, a kind of method that forms the conductivity meter facial mask is provided.This method comprises:

Electrically conductive composition is provided; And

This electrically conductive composition is applied to carrier.

In yet another embodiment, a kind of method that forms matrix material is provided.In one embodiment, this method comprises this surface film of co-curing and composite prepreg.In another embodiment, this method comprises this surface film is bonded to matrix material.

Description of drawings

Fig. 1 is the schema that forms the embodiment of the method for conducting electricity thermoset composition and forming article;

Fig. 2 is the schema of embodiment that is formed the method for matrix material by the embodiment of conduction thermoset composition;

Fig. 3 is a synoptic diagram of integrating the prepreg lamination of the surface film that the embodiment by the conduction thermoset composition forms;

Fig. 4 A is sem (SEM) Photomicrograph that comprises the surface film xsect of silver-colored sheet conducting additive, and it shows that silver-colored thin slice takes the stratiform pattern;

Fig. 4 B is the SEM Photomicrograph of the fracture surface of the surface film that formed by the conductive polymer compositions embodiment that comprises silver-colored thin slice;

Fig. 5 A figure that to be resistivity change with the conductive additive of the surface film that is formed by conduction thermoset composition embodiment;

Fig. 5 B figure (comprising graphitized carbon black and carbon nanofiber) that to be resistivity change with the concentration of the surface film that is formed by conduction thermoset composition embodiment;

Fig. 6 figure that to be resistivity change with the concentration of two kinds of silver-colored thin slices of difference of the surface film that is formed by conduction thermoset composition embodiment;

Fig. 7 figure that to be resistivity change with the concentration of the silver-colored thin slice of the surface film that is formed by conduction thermoset composition embodiment (separately and and other conductive additives (nano silver wire, carbon nanotube and metal coat ball));

Fig. 8 A-8B is the front view of composite panel after regional 1A lightning test that adds surface film; (A) without painted synopsis facial mask; (B) contain the surface film of silver-colored thin slice without painted;

Fig. 9 A-9B is the front view of composite panel after regional 1A lightning test that adds surface film; (A) through painted synopsis facial mask; (B) contain the surface film of silver-colored thin slice through painted;

Figure 10 A-10B is the front view of composite panel after regional 2A lightning test that adds surface film; (A) contain the surface film of silver-colored thin slice without painted; (B) contain the surface film of silver-colored thin slice through painted.

Embodiment

Term used herein " approximately ", " pact " and " basically " representative still can be implemented desired function or reach the amount of the approaching said amount of expected result.For example, term " approximately ", " pact " and " basically " can refer to less than 10%, less than 5%, less than 1%, less than 0.1% and less than the amount in 0.01% the said weight range.

Term used herein " room temperature " has the common implication that those skilled in the art of the present technique know, and can be included in about 16 ℃ (60 ℉) to the interior temperature of 32 ℃ of (90 ℉) scopes.

Term used herein " fiber " has the common implication that those skilled in the art of the present technique know, and can comprise one or the multiple filamentary material that is suitable for reinforced composite material.Fiber can be taked whisker, staple fibre, continuous fibre, monofilament, fibrous bundle, bundle, sheet, layer and array configuration thereof.That continuous fibre can further adopt is unidirectional, multidimensional (for example two dimension or three-dimensional), non-woven, weave, knitting, stitching, coiling and knitting structure and revolve pad, felt pan and shortly cut any in the mat structure.The weaving fiber structure can comprise and has less than about 1000 monofilament, less than about 3000 monofilament, less than about 6000 monofilament, less than about 12000 monofilament, less than about 24000 monofilament, less than about 48000 monofilament, less than about 56000 monofilament with less than a plurality of weaving fiber bundles of about 125000 monofilament.In more another embodiment, fibrous bundle can remain on the appropriate location through cross-fiber bundle suture, the weft knitting knitting suture of insertion or low amounts of resin (for example thermoplastic resin).

The composition of fiber can optionally change.Fibrous instance can include but not limited to glass; Carbon; Aromatic poly; Quartzy; Vilaterm; Polyester; Polyparaphenylene benzoxazole (PBO); Boron; Polymeric amide; Carbon and graphite; Silit; Silicon nitride; Astroquartz

; Tyranno ; Nextel

; Nicalon

; And compsn.

Term used herein " resin " has the common implication that those skilled in the art of the present technique know, and can comprise one or more compounds that comprise thermoset and/or thermoplastic material.Instance can include, but are not limited to epoxy resin, epoxy curing agent, phenolic resins, phenol, cyanate, polyimides (for example, BMI (BMI) and PEI), polyester, benzoxazine, polyphenyl and oxazines, polyphenyl and dislike ketone, polybenzimidazoles, polybenzothiozole, polyamide, polyamidoimide, polysulfones, polyether sulfone, Merlon, PET, cyanate, cyanate and polyether-ketone (for example polyether-ketone (PEK), polyether-ether-ketone (PEEK), PEKK (PEKK) and like that), its combination and precursor thereof.

Epoxy resin can comprise further that each molecule has the polyepoxides at least about two epoxide groups.That this polyepoxides can be is saturated, undersaturated, ring-type or non-annularity, aliphatics, alicyclic, aromatic series or heterocycle.The instance of suitable polyepoxides comprises polyglycidyl ether, and it prepares through epoxy chloropropane or epoxy bromopropane and polyphenol are reacted in the presence of alkali.The polyphenol that is applicable to this does; For example Resorcinol, pyrocatechol, Resorcinol, dihydroxyphenyl propane (two (4-hydroxy phenyls)-2; 2-propane), Bisphenol F (two (4-hydroxy phenyl) methane), two (4-hydroxy phenyl)-1,1-Trimethylmethane, 4,4 '-dihydroxy benaophenonel, two (4-hydroxy phenyl)-1; 1-ethane and 1,5-hydroxyl naphthalene.Other polyphenol on suitable basis as polyglycidyl ether are the known phenolic resin type condensation product of phenol and formaldehyde or acetaldehyde.

Other polyepoxidess can comprise the polyglycidyl ether of polyvalent alcohol or diamines.This type of polyglycidyl ether is derived from polyvalent alcohol, for example terepthaloyl moietie, Diethylene Glycol, triethylene glycol, 1,2-Ucar 35,1,4-butyleneglycol, triethylene glycol, 1,5-pentanediol, 1,6-pinakon or TriMethylolPropane(TMP).

Other polyepoxides can comprise the poly glycidyl ester of polycarboxylic acid, for example the reaction product of Racemic glycidol or epoxy chloropropane and aliphatics or aromatic series polycarboxylic acid (for example oxalic acid, succsinic acid, pentanedioic acid, terephthalic acid or dimer (fatty acid) yl).

Other epoxy compoundss can comprise derived from the epoxidation product of the unsaturated cycloaliphatic compounds of ethylenic or derived from those of natural oil & fat.

Other epoxy compoundss can comprise the liquid epoxies that obtains through dihydroxyphenyl propane or Bisphenol F and epichlorohydrin reaction.At room temperature has epoxy equivalent (weight) weight usually from 150 to about 480 for the epoxy resin of liquid.

Also can (or another is chosen as) use at room temperature to be solid epoxy resin, and can obtain from polyphenol and epoxy chloropropane equally, for example based on the epoxy resin of dihydroxyphenyl propane or Bisphenol F have from 45 to 130 ℃, preferably from 50 to 80 ℃ fusing point.The difference of this solid epoxy and liquid epoxies is to have higher molecular weight basically, so it at room temperature is a solid.Solid epoxy has the epoxy equivalent (weight) weight more than or equal to about 400 usually.

Term used herein " curing " has the common implication that those skilled in the art of the present technique know, and can comprise polymerization and/or cross-linking process.Curing can be implemented in interior process through including but not limited to heat, be exposed to UV-light and be exposed to radiation.In certain embodiments, curing can take place in the substrate.Before solidifying, it is one or multiple compound of liquid, semisolid, crystalline solid and combination thereof that matrix can further be included under about room temperature.In more another embodiment, the matrix in the prepreg can be solidified to present selected viscosity or viscosity by the part warp.In certain embodiments, can in single process, implement fixed and curing.

Term used herein " fixed " has the common implication that those skilled in the art of the present technique know, and can comprise that resin wherein or substrate material flow so that in the alternative fiber and the process of adjoining the void space of fiber.For example, " fixed " can include but not limited to make matrix flow into fiber and prepreg and like that between and the void space of inside." fixed " can and one of exert pressure or many persons act on down and further taking place in heat, vacuum.

Term used herein " dipping " has the common implication that those skilled in the art of the present technique know, and can be included in one or multiple fiber between or adjoin one or multiple fiber introduce substrate material.Matrix can be taked the form of film, powder, liquid and combination thereof.Can be through one of applying in heat, pressure and the solvent or many persons help dipping.

Term used herein " prepreg " has the common implication that those skilled in the art of the present technique know, and can comprise fibre plate or the thin layer that has been impregnated with substrate material.Matrix can also exist by partly solidified state.

Term used herein " lamination " and " prepreg lamination " have the common implication that those skilled in the art of the present technique know, and can comprise one or a plurality of preimpregnation bed of materials that adjoin placement each other.In certain embodiments, the preimpregnation bed of material in the lamination can be relative to each other with selected to the location.For example, the prepreg lamination can comprise the preimpregnation bed of material with unidirectional fibre framework, and wherein fiber is directed with 0 °, 90 °, selected angle θ and combination thereof with respect to the overall dimension (for example length) of lamination.Should be further appreciated that in certain embodiments, can merge prepreg to form the prepreg lamination with arbitrary conjugate fiber framework (for example unidirectional and multidirectional).

In yet another embodiment, can choose wantonly with wear wire material with the prepreg layered suture lump together depart to suppress its relative movement selected to.Lamination can be through including but not limited to manual lamination, arranging that with lamination (ATL), high fiber (AFP) and monofilament are wound on interior technology and make automatically.

Embodiment of the present invention are provided for the conduction thermoset composition and the respective production method of surface film and tackiness agent.Under the situation of not using buried metal net or paper tinsel, the surface film that is formed by said composition has the warp enhancing electroconductibility of working as with metallographic phase.This type of surface film can pass through, for example co-curing adds composite structure (for example prepreg, adhesive tape and fabric) as the outermost surface layer.In this way, when this surface film is used for such as application such as aircraft components as outmost conductive layer, the shielding of lightning Protection (LSP) and electromagnetic interference (EMI) can be provided.

In certain embodiments; The enhanced electroconductibility of surface film can be reached through thermosetting polymer and conductive additive are made up, and this conductive additive is for for example be scattered in the whole film or be scattered in sheet metal and/or the conductive nano-particles on the film basically equably.Valuably, the wire netting that these compsns can reduce use phase counterweight basically comes the needs of the electroconductibility of enhanced surface film, makes weight reduce basically.For example, there is the conductivity meter facial mask of wire netting to compare, can reaches about weight savings of 50 to 80% with embedding.In surface film embodiment disclosed herein, there are not this type of net and paper tinsel, can further help to be easy to make, and reduce the cost that uses this surperficial film formed composite material assembly.

Particularly, the embodiment of having found to comprise the polymer compsn of silver-colored sheet conducting additive presents remarkable enhanced electroconductibility.Such as hereinafter argumentation, do not desire to be subject to theory, we think that silver-colored thin slice is taked interconnective basically layered struture in whole compsn under selected concentration (for example greater than about 35 weight %).This layered struture provides surface film with uniform continuous conduction path and high conductivity/low-resistivity basically relatively.For example, can reach and planar have about 10 surface film to the resistivity value of 50 milliohms/square number magnitude.Can further make the resistivity of this surface film be reduced to about 0.2 value such as other conductive additives such as nano silver wires through adding to 15 milliohms/square number magnitude.It should be noted that these resistivity and work as such as metallographic phase such as aluminium (for example about 0.2 milliohm/square), show that use replaces the heavier feasibility that contains the surface film of net by the surface film that electrically conductive composition embodiment disclosed herein forms.

Type that also can be through regulating conductive additive and/or the embodiment that amount makes electrically conductive composition satisfy the requirement of various application.For example, if to be enough to that compsn is had between about 1 ohm-sq to 1 * 10 ⁸The concentration of the surface resistivity in the ohm-sq scope provides conductive additive, then can strengthen the Electrostatic Discharge protection.In another example, if to be enough to that compsn is had between about 1 * 10 ^-6Ohm-sq to 1 * 10 ⁴The concentration of the surface resistivity in the ohm-sq scope provides conductive additive, then can strengthen the electromagnetic interference (EMI) shielding protection.In a further example, if to be enough to that compsn is had between about 1 * 10 ^-6Ohm-sq to 1 * 10 ^-3The concentration of the surface resistivity in the ohm-sq scope provides conductive additive, then can strengthen lightning Protection (LSP).

In more another embodiment, also can surface film be added in the matrix material.For example, surface film can be through being incorporated in the matrix material with prepreg (for example about 250 ℉ and 350 ℉ solidify prepreg) co-curing, so that the composite structure with excellent surface smooth finish and high conductivity to be provided.In alternate embodiment, can make surface film and at solidified matrix material secondary bond under the temperature between about 160 ℉ and 350 ℉.Advantageously, this makes handiness tolerable during matrix material is made or afterwards surface film is incorporated in the composite structure.Also can be adjusted in the scope of about 140 ℉ and 360 ℉ to the solidification value of the outer solidified prepreg of cryogenic high pressure still with the surface film embodiment.Hereinafter is discussed these and other advantage of the embodiment that discloses in detail.

Fig. 1 shows an embodiment of the method 100 of making matrix material, and this matrix material adds to comprise and conducts electricity the surface film of thermoset polymer compositions.Method 100 comprises following operation: in square frame 102, in mixing vessel, add one or more and can form the resin of thermosetting polymer; In square frame 104, in mixing vessel, add one or more conductive additive; In square frame 106, in mixing vessel, add one or more non-conducting filler, flow control agent, chain extension agent and/or pigment; In square frame 110, in mixing vessel, add one or more UV stabilizer; In square frame 112, in mixing vessel, add one or more and be used for the solidifying agent and/or the catalyzer of resin; And in square frame 114, the compsn coarse filtration is also outgased.Method 100 can further comprise makes compsn form one in surface modes (in square frame 116) or the tackiness agent (in square frame 120).Method 100 can further be included in the square frame 122 surface film is incorporated in the matrix material.

Discuss in detail like hereinafter, in method 100, can each component of compsn be added into through equipment to be used for mixing, heating and/or cool off the mixing vessel of this component.In addition, also can optionally one or more solvent be added in the mixture to promote the mixing of each component.The instance of this kind solvent can include but not limited to methyl ethyl ketone (MEK), acetone, N,N-DIMETHYLACETAMIDE (DMAc) and N-Methyl pyrrolidone (NMP).Should be appreciated that method 100 can comprise more or less step, and the step of method 100 can be implemented with arbitrary order optionally.

Such as among Fig. 1 displaying, in square frame 102, thermosetting resin is added in the mixing vessel.The instance of thermosetting resin can include but not limited to the resin that preceding text are for example discussed.In preferred embodiments, thermosetting resin can comprise one or more in epoxy resin, bismaleimides (BMI), cyanate, resol, benzoxazine and the polymeric amide.In other embodiments, thermosetting resin can comprise diglycidylether and four glycidyl ether methylene dianiline (MDA)s, the 4-glycidyl oxygen base-N of diglycidylether, the tetrabromo-bisphenol of dihydroxyphenyl propane, N '-2-glycidyl aniline and combination thereof.Thermosetting resin can further comprise chain extension agent and toughner.In one embodiment, thermosetting resin can exist based on the concentration of gross weight between about 5 weight % to 95 weight % of compsn.In other embodiments, thermosetting resin can exist between the concentration between about 20 to 70 weight %.

Also can in mixing vessel, add the extra heat thermosetting resin to regulate the viscosity and the drape of compsn.The instance of this resinoid can include, but is not limited to polyfunctional epoxy resin.The instance of two senses and polyfunctional epoxy resin can include, but is not limited to commercial resins, the product of for example selling with trade(brand)name MY 0510, MY9655, Tactix 721, Epalloy 5000, MX 120, MX 156.This extra epoxy resin can exist based on the amount of gross weight between about 0 to 20 weight % of compsn.

After being added into thermosetting resin or polymkeric substance in the mixing vessel, can use the high speed shear mixing machine to come blend mixture.Can implement to mix mixes evenly basically until thermosetting resin.For example, in one embodiment, the speed that mixing can about 1000rpm to 5000rpm was implemented about 50 minutes to 70 minutes.

In other embodiments, also can in square frame 102, in compsn, add film rigidity and the surface hardness of toughner with the reconciliation statement facial mask.In certain embodiments; The characteristic of toughner can be polymeric or oligomerization; It has be lower than 20 ℃ (more preferably less than 0 ℃ or be lower than-30 ℃ or be lower than-50 ℃) second-order transition temperature; And/or have when through heating when solidifying the present composition can with the functional group of other component reaction of the present composition, for example epoxide group, hydroxy-acid group, amino and/or hydroxyl.In certain embodiments, toughner can comprise the elastic body toughening agent.In other embodiments, toughner can comprise nuclear-shell rubber grain or fluid rubber.The instance of toughner can be referring to USP the 4th, 980, and No. 234, U.S. Patent application discloses No. 2008/0188609 and the open case of international monopoly WO/2008/087467 number, the mode that this case is quoted in full is incorporated herein.Based on the gross weight of compsn, the concentration of toughner can be between about 5 weight % to 40 weight %.The concentration of toughner can be further between about 1 weight % to 30 weight %.

Other instance of elastic body toughening agent (for example can include, but is not limited to carboxylated nitrile; Nipol 1472; Zeon Chemical), the polyhutadiene (CTB) of the butadiene acrylonitrile of carboxy blocking (CTBN), carboxy blocking, polyethersulfone (for example, KM 180 PES-Cytec), PEEK, PEKK thermoplastic material and nuclear/shell rubber grain (for example the MX 120 of Kaneka, MX 156 and have pre-dispersed nuclear/other MX resin of shell rubber nano particulate).

In square frame 104, can in mixing vessel, add conductive additive.The embodiment of conductive additive can include, but is not limited to metal and metal alloy, is coated with metallic particle, the metal through functionalisation of surfaces, conduction hovel, nonmetal, polymkeric substance and nanometer materials.The form of conductive additive can comprise thin slice, powder, particle, fiber and like that in one or more.In one embodiment, based on the gross weight of compsn, the total concn of all conductive additives can be between about 0.1 weight % to 80 weight %.In alternate embodiment, the concentration of all conductive additives can be between about 0.5 weight % to 70 weight %.

Metal and alloy thereof can be used as effective conductive additive owing to having high relatively electroconductibility.Can be used for the metal of embodiment of the present invention and the instance of alloy and can include, but is not limited to silver, gold, nickel, copper, aluminium and alloy thereof and mixture.In certain embodiments, the form of conducting metal additive can comprise one or more (alone or in combination) in thin slice, powder, fiber, line, microsphere and the nanometer spheroid.

In certain embodiments, can use such as precious metals such as Jin Heyin, this is because of its stability (for example, anti-oxidant) and renders a service.In other embodiments, because the price of silver is lower, so can use silver with the metallographic ratio.Yet, should be appreciated that, in the system that the silver migration possibly throw into question, alternately use gold.Valuably, such as hereinafter argumentation, be filled with silver with the gold epoxy resin can reach less than about 20 milliohms/square resistivity.

In other embodiments, conductive additive can comprise and is coated with metallic particle.The instance that is coated with metallic particle can comprise the glass sphere that is coated with metal, be coated with the graphite of metal and be coated with the fiber of metal.The instance that can be used as the metal of substrate or coating can include, but is not limited to silver, gold, nickel, copper, aluminium and composition thereof.

In more another embodiment, conductive additive can comprise the conduction hovel.The carbon pad that the instance of this type of conduction hovel can include, but is not limited to be coated with non-woven hovel, wire netting/paper tinsel, the carbon pad of metal or be coated with metal.The instance of spendable metal can include, but is not limited to silver, gold, nickel, copper, aluminium and composition thereof.

The suitable nonmetal embodiment that is used as the conductive additive of the embodiment of the invention can include, but is not limited to graphitized carbon black, graphite, weisspiessglanz, thomel.

The instance of the nano material of suitable conductive additive as embodiment of the present invention can comprise carbon nanotube, carbon nanofiber, be coated with carbon nanofiber, metal nanometer line, metal nanoparticle, graphite (for example Nano graphite platelet) and the nano chain (nanostrand) of metal.In certain embodiments, the average largest dimensions of nano material can be less than 100nm.

Carbon nanotube can comprise SWCN (SWNT), double-walled carbon nano-tube (DNT) and multi-walled carbon nano-tubes (MWNT).Also can choose wantonly carbon nanotube is carried out functionalisation of surfaces.The instance that can be used for the functionalized functional group of carbon nanotube can include, but is not limited to hydroxyl, epoxy group(ing) and amine functional group.Other instance through functionalized carbon nanotubes can comprise the Nano-In-Resin from Nanoledge, and it is a CNT/ epoxy resin enriched material, and wherein CNT is pre-dispersed in epoxy matrix material.

The instance of the carbon nanofiber of suitable conductive additive as embodiment of the present invention can comprise naked carbon nanofiber (CNF), the CNF that is coated with metal and NanoBlack II (Columbian Chemical, Inc.).Metallic paint can include, but is not limited to copper, aluminium, silver, nickel, iron and alloy thereof.

The instance of the nano wire of suitable conductive additive as the embodiment of the invention can include, but is not limited to nickel, iron, silver, copper, aluminium and alloy thereof.The length of this nano wire can be greater than about 1 μ m, greater than about 5 μ m, greater than about 10 μ m and about 10-25nm.The diameter of this nano wire can be greater than about 10nm, greater than about 40nm, greater than about 70nm, greater than about 150nm, greater than about 300nm, greater than about 500nm, greater than about 700nm and greater than about 900nm.The instance of nano silver wire can comprise from the SNW-A60 of Filigree Nanotech company, SNW-A90, SNW-A300 and SNW-A900.

In a preferred embodiment, conductive additive can comprise silver-colored thin slice.Discuss in detail like hereinafter, have recognized that, use the combination of silver-colored thin slice, especially silver-colored thin slice and nano silver wire, can the electroconductibility of thermoset composition significantly be enhanced to and be substantially equal to or greater than the level of the electroconductibility of metal.In addition, can other conductive additive that silver-colored thin slice and this paper discussed be made up the electroconductibility with further enhancing thermoset composition.Instance includes, but is not limited to nano wire (for example, nano silver wire), carbon nanotube, is coated with the glass sphere of metal (for example, being coated with the glass sphere of silver).

For example, comprise that the resistivity of the compsn embodiment of silver-colored thin slice can be from based on the heap(ed) capacity (adding the nano silver wire of about 3 weight %) of the about 63 weight % of the gross weight of compsn the time be low to moderate about 0.2 milliohm/square to the heap(ed) capacity (adding independent silver-colored thin slice) of about 18 weight % the time greater than about 4500 milliohms/square do not wait.The ability of the resistivity of adjustment compsn is very important in this broad range, because the loading percentage of conductive additive is to be used for any one that ESD, EMI and LSP use in the adjustable compositions.

Fig. 4 A-4B provides the polished cross-sections of look-up table facial mask and the SEM Photomicrograph of fracture surface, and this surface film contains the surface film embodiment that in epoxy matrix material, comprises silver-colored thin slice (clear zone, Fig. 4 A).Inspection from Fig. 4 A can be observed, and the xsect of silver-colored thin slice is elongated usually, has high aspect ratio and is distributed in equably in the whole compsn basically.In addition, silver-colored thin slice contacts with each other, and forms successive network basically.This interconnective layered struture is through the fracture surface of look-up table facial mask be confirmed (Fig. 4 B).This representative Photomicrograph demonstration is present on the fracture surface in whole fracture surface basically or ruptures the outstanding silver-colored thin slice in surface certainly.

In certain embodiments, as discussing in detail among the hereinafter embodiment, this stratiform pattern can use silver-colored thin slice with about 3 μ m to 36 μ m mean sizes with greater than about 30 weight %, for example the concentration of about 39 weight % to 65 weight % is reached.Do not desire to be subject to theory, we think that this conductive path is to make in this conductivity meter facial mask, to reach basically the reason of high conductivity uniformly.The bigger thin slice size (up to about 30 μ m) of silver thin slice provides abundant surface-area to contact with relatively large surface-area, in whole compsn, on X-Y and Z both direction, to reach the successive satisfactory electrical conductivity.

The layered struture and the extraordinary electroconductibility of silver thin slice are all unexpected.Such as hereinafter embodiment argumentation, this type of metallike electroconductibility is guaranteed to conduct electricity thermoset composition and is had and be applicable to the superperformance of using such as the surface film that is used for lightning Protection etc.

In square frame 106, can in mixing vessel, add non-conducting filler.In certain embodiments, the overall dimension of this filler can be between about 12 to 150 μ m.This filler can further exist with the amount of gross weight between about 0 weight to 40 weight % based on compsn.In other embodiments, this filler can exist between the concentration between about 5 weight % to 30 weight %.

The instance of non-conducting filler can comprise that chalk grinding or sedimentary, quartz powder, aluminum oxide, rhombspar, thomel, spun glass, polymer fiber, titanium oxide, fused silica, carbon black, quicklime, magnesium calcium carbonate, tiff reach the especially silicates filler of magnalium calcium-silicate type.More argumentations of filler can be referring to USP the 4th, 980, No. 234.

In other embodiments, non-conducting filler can include, but is not limited to ceramic microspheres (for example, Zeeosheres-3M), glass sphere (for example, iM30K, A16, H20-3M Corp.; SID-230Z-S2-Emersion & Cummings) and pyrogenic silica.Filler can be solid and provides with thin slice, powder, fiber, microsphere or glass sphere form, and can optionally be solid or hollow structure.In one embodiment, filler can comprise ZEESPHERES 200 ^TM, it is the hollow heavy wall spheroid of silica-alumina ceramic composition.

Also can in compsn, add chain extension agent to increase the molecular weight of compsn.Based on the gross weight of compsn, the concentration of chain extension agent can be between about 1 weight % to 30 weight %.The instance of chain extension agent can comprise dihydroxyphenyl propane, tetrabromo-bisphenol (TBBA), bisphenol Z, tetramethyl-dihydroxyphenyl propane (TMBP-A) and other bis-phenol fluorine, like USP the 4th, 983, is discussed in No. 672.

Can in compsn, add color and the outward appearance of pigment with the reconciliation statement facial mask.In one embodiment, pigment can comprise titanium oxide, carbon black, black pigment and other color dye.This pigment can thin slice, the form of powder, fiber, color enriched material liquid provides.Based on the gross weight of compsn, the total amount of all pigment can be between about 0 weight to 20 weight %.

Also can in square frame 106, in mixing vessel, add flow control agent.Can use this flow control agent to regulate the rheological property of compsn.The embodiment of flow control agent can include, but is not limited to pyrogenic silica, microsphere and metal-powder.This flow control agent can thin slice, powder, fiber, spheroid or particle shape formula provide.The overall dimension of this flow control agent can be between about 0.5 to 10 μ m.This flow control agent can be based on the gross weight of compsn between about 0 weight to 40 weight %, more preferably the amount between about 0.1 weight % to 10 weight % exists.

After in mixing vessel, adding conductive additive and adding any one in filler, pigment, chain extension agent and/or the flow control agent, mixture is mixed so that this component is distributed in the compsn basically.In certain embodiments, the speed that mixing can about 500rpm to 5000rpm was implemented about 60 minutes to 120 minutes.During mixing process, also can make the temperature of compsn keep below about 160 ℉ or be lower than the temperature of the chemical reaction that possibly take place not expect.

In square frame 110, can choose wantonly and in mixture, add UV stabilizer.The embodiment of UV stabilizer can comprise UV light absorber, inhibitor, pigment, blocker (blocking agent) and filler.The instance of UV stabilizer can include, but is not limited to Yoshinox BHT (BHT), 2-hydroxyl-4-methoxyl group-UVNUL MS-40 (UV-9), 2; 4-two (2; The 4-3,5-dimethylphenyl)-6-(2-hydroxyl-4-octyl group oxygen base phenyl)-1; 3; 5-triazine (CYASORE

UV-1164 light absorber), 3,5-di-tert-butyl-4-hydroxybenzoic acid, n-hexadecyl ester (CYASORB UV-2908 photostabilizer), titanium oxide and carbon black.This UV stabilizer can solid or liquid form provide.In one embodiment, UV stabilizer can exist with the amount of gross weight between about 0.1 weight % to 5 weight % based on compsn separately.In other embodiments, UV stabilizer can exist with the amount of gross weight between about 0.5 weight % to 3 weight % based on compsn separately.

After in mixing vessel, adding the UV stabilizer regulator, speed that can about 500rpm to 2000rpm is mixed mixture about 30 minutes to 60 minutes.Also can make the temperature of compsn keep below about 160 ℉.

In square frame 112, can in mixture, add solidifying agent and the optional catalyzer that exists.In certain embodiments, solidifying agent can make the epoxy resin of compsn in the TR of about 250 ℉ to 350 ℉, solidify.One or more solidifying agent can exist based on the amount of gross weight between about 0.1 weight % to 40 weight %, preferred about 0.5 weight % to 10 weight % of compsn.

The instance of solidifying agent and catalyzer can include, but is not limited to aliphatics and primary aromatic amine, aliphatics and aromatic nitrile base, boron trifluoride mixture, guanidine and Dyhard RU 100.Other instance of solidifying agent and catalyzer can be referring to USP the 4th, 980, and No. 234 and U.S. Patent application disclose No. 2008/0188609.

Other instance of amine hardener and catalyzer (for example can include, but is not limited to Dyhard RU 100, allophanamide; 2; 4-toluene is two-(dimethyl urea) [Omicure U-24 or CA150], 4,4 '-methylene-bis-(phenyl dimethyl urea) [Omicure U-52 or CA152] is sold by CVC Chemicals)), and 4; 4 '-diamino diphenyl sulfone (4,4-DDS) and BF ₃

In certain embodiments, during solidifying agent and catalyzer interpolation, can make the temperature of compsn keep below set point value, to suppress causing resin chain extension (resin advancement) because of catalyzer begins to decompose to reach with resin reaction too early.The chosen temperature value can for example, be lower than about 130 ℉ between about 75 ℉ to 150 ℉.In other embodiments, implement shear-mixed with the speed between about 500rpm to 2000rpm.

Table 1 provide can be used as surface film and tackiness agent such as preceding text the selected embodiment of argumentation conductive polymer compositions.

The embodiment of table 1-conductivity meter facial mask and binder compsn

In square frame 114, can be ready to compsn and supply to use.In one embodiment, can carry out coarse filtration to filter out any impurity and the oversize granule in the compsn to compsn.In certain embodiments, can filter compsn to remove external fragment and the oversize granule in the compsn through reticulattion with selected aperture size.

In more another embodiment, can implement the degassing to remove the bubble that possibly be incorporated in the composition in its entirety basically to compsn in a vacuum.In one embodiment, can apply about 26 inches vacuum to compsn to 30 inches mercury.Should be appreciated that, in degasification process, also can remove the volatile matter content of the selected part of compsn.In certain embodiments, can implement to outgas so that have the solids content of about 55 weight % to 100 weight % based on the TV of compsn through the compsn that outgases.

Prepared compsn can be used for multiple application subsequently.Limiting examples can comprise surface film (square frame 116), add the matrix material (square frame 120) and the tackiness agent (square frame 122) of surface film.

In square frame 114, can make compsn form surface film subsequently.In certain embodiments, heat fusing coating capable of using or solvation film coating procedure apply film forming with compsn.The gained film can have the film weight of between about 0.01psf to 0.15psf (for example, about 0.035psf).

Can be further the embodiment of surface film be applied to supporting structure, for example helps the carrier of processing list facial mask.The instance of supporting structure can comprise wire netting or paper tinsel, non-woven mat, unordered pad, knitting carrier, be coated with the carbon hovel of metal and like that.The geometrical shape of supporting structure can optionally change.For example, the thickness of carrier can be between Mill, about 0.5 Mill to 5.Other parameter (the for example open amount of per unit area, chain width and pattern) about this carrier also can optionally change.

The instance of wire netting or paper tinsel can comprise expanded metal net or paper tinsel and be coated with the hovel of metal.This net and paper tinsel can comprise copper, aluminium, silver, nickel and alloy thereof.

The instance of non-woven mat carrier can comprise carbon pad, polymer pad and be coated with the carbon of metal, glass or polymer glass hovel.This non-woven mat carrier can be coated with copper, aluminium, silver, nickel, reach alloy and alloy thereof.

Can implement dry subsequently to remove volatile matter to the film of formation like this.In certain embodiments, based on the gross weight of film, the content of the volatile matter of film can be between about 0.1 weight % to 0.99 weight %.For example, the content of the volatile matter of drying back surface film can be less than about 1 weight %.

Also can store the surface film of formation like this, until needs.For example, surface film can be stored in the refrigerator chamber and solidify to suppress surface film, prolongs its available depositing the frame life-span.Can one or more surface that backing film or paper are applied to surface film be gone up to suppress surface film and be attached to the surface unintentionally before using drafting.

In square frame 116, can surface film further be integrated in the composite structure.This process is discussed with reference to Fig. 2 and 3 hereinafter in further detail.Fig. 2 shows an embodiment of the method 200 that forms the matrix material that comprises surface film embodiment of the present invention.The corresponding schematic diagram shows of this matrix material is in Fig. 3.

In square frame 202, mould or instrument 314 (Fig. 3) can be through preparation to admit surface film 310 and composite prepreg laminated 304.Mould 314 can be constructed with selected shape and can optionally further comprise texture and/or other surface and perforation thickness characteristics.Prepreg laminated 304 and/or surface film 310 can contact with at least a portion of mould 314 through placing, thus can such as hereinafter argumentation with composite material solidification in the mould 314 of selecting shape.Can on instrument, apply abrasive to remove surface patches and to obtain slick basically surface.Can in mould 314, further apply releasing agent shifts out composite part with after helping to finish dealing with from mould 314.

In square frame 204, surface film 310 is applied to mould 314.Can surface film 310 be taken out and be warming up to about room temperature in refrigerator chamber.Subsequently surface film 310 is cut into intended shape, and removes the backing film on the side of the enrichment resin that is positioned at surface film 310.Subsequently exposed film is applied on the clean surface of mould 314, should notes making not having fold or bubble in the surface film 310 basically.Apply in this way surface film 310 can through manually or robotization machine-processed (for example, being with laminated (ATL), automatic fibers to arrange (AFP) automatically) accomplish.

In square frame 206, can be with prepreg laminated 304 and surface film co-curing so that surface film 310 be incorporated in the matrix material.In one embodiment, can one or more preimpregnation bed of material be assemblied in surface film 310 and adjoin in the prepreg laminated 304 of placement.In alternate embodiment, can assemble prepreg laminated 304 and adjoin placement with surface film 310 subsequently.Prepreg can optionally be taked the form of Woven fabric or band.

Randomly, can insert one or more core 320 at each interlayer of prepreg laminated 304.This core can comprise foaming structure, honey-combed and like that.Can between prepreg laminated 304 and core 320, further insert binder film 326, be bonded to prepreg laminated 304 to help core 320.

Can further adjoin the surface of the prepreg laminated 304 relative and place fep film 330 with surface film 310.Fep film 330 provides isolates and parts release.

Also can adjoin the surface of fep film 330 and place air-permeable mattress 332.Air-permeable mattress 332 is used for being absorbed by prepreg laminated 304 at least a portion of excess resin.Although do not show, as is known to the person skilled in the art, also can in institute's assembly structure, add ventilative cloth.

Can the assembly that form in this way 308 be encapsulated in and can keep in the casing material of the vacuum that is applied, and be positioned over be used to solidify and/or the laminated encapsulation object 300 with surface film 310 embodiments of fixed prepreg in.In certain embodiments, encapsulation object 300 can be through structure to provide heat 308, pressure 302, vacuum 316 and combination, for example baking oven and autoclave.

In the embodiment of heating assembly 308, look used the drafting solidification value of prepreg resin and decide, can encapsulation object 300 be heated between about 180 ℉ to 350 ℉, the preferred temperature between about 250 ℉ to 350 ℉.In certain embodiments, heating rate can be between about 1 to 5 ℉/min.

In more another embodiment, encapsulation object 300 can apply vacuum to assembly 308.For example, casing material 312 can form the roughly resistance to air loss zone that is communicated with the vacuum source of encapsulation object 300.The vacuum level that is applied by encapsulation object 300 solidify and/or fixed during can change to some extent or keep constant.For example, can apply between about 40psi to 50psi or littler vacuum to assembly 308.

In more another embodiment, encapsulation object 300 can exert pressure 302 to assembly 308.Institute's applied pressure 302 can be provided by the pressure source that is communicated with encapsulation object 300.In addition, institute's applied pressure 302 solidify and/or fixed during can change or keep constant.For example, can look parts design and structural integrity and apply the pressure between about 14psi to 100psi.

In square frame 210, can implement polishing operation to surface film.In one embodiment; Can (for example on surface film, apply the fine grinding agent; About 240 to 320 granularities), and the roughness or the polishing degree of selected degree are provided to the surface of surface film 310 removing the lip-deep any fragment (for example, releasing agent) that is positioned at surface film 310 basically.Surface treated composite structure can apply priming and top coating silk thinkling sound.

Embodiment

Discuss surface film hereinafter among the embodiment in detail from the embodiment formation of conduction thermoset composition of the present invention.Particularly, research contains electroconductibility and/or resistivity and the lightning Protection performance that this surface film provided of the surface film of various conductive additives, and compares with other system.It should be noted that and find that the compsn that contains silver-colored thin slice (making up separately or with other conductive additives) presents low-down resistivity value of working as with metallographic phase.These embodiment discuss from the exemplary purpose, should not be construed as the scope of the disclosed embodiment of restriction.

The preparation of embodiment 1-surface modes

The thermoset electrically conductive composition that is used for surface film is to prepare from the component that hereinafter table 2 is listed.Each self-contained epoxy resin of said composition, elastic body toughening agent, non-conductive additive, flow control agent, UV stabilizer, solvent and conductive additive.Each research conductive additive among the test 1-6 is to the influence of the resistivity of surface film.

Table 2-surface film compsn

The conductivity meter facial mask is to prepare through in mixing vessel, adding the component that preceding text list and using high speed shear laboratory mixing machine to mix said component.The epoxy resin of about 100 parts by weight is added in the mixing vessel; The diglycidylether (DER 331-Dow Chemical) that comprises the dihydroxyphenyl propane of about 60: 40: 10 ratios: four glycidyl ether methylene dianiline (MDA)s (MY9655-Huntsman): the diglycidylether of tetrabromo-bisphenol (DER 542-Dow Chemical), and under about 1000rpm stir about 30 minutes.If desired, MEK adds to regulate the rheological property and the solids content of compsn with epoxy resin as solvent.

Subsequently, in epoxy resin, add the elastic body toughening agent Nipol 1472 (Zeon Chemical) of about 1.5 weight % and CTBN (or CTB) the type elastomerics (Hycar CTBN 1300X13-Noveon) of 1.5 weight %.Also in this mixing vessel, add conductive filler material with the concentration of about 46-56 weight %.The flow control agent, the amorphous pyrogenic silica that further in this mixing vessel, add the ceramic microspheres (Zeeospheres G-200-3M.) of about 10 weight %, about 2 weight % reach about separately 1% UV stabilizer BHT and 2-hydroxyl-4-methoxyl group-UVNUL MS-40.Optionally add the MEK solvent, with the viscosity controller of above mixture solid, and each component of compsn mixed under about 1000-3000rpm about 50-70 minute to about 80 weight %.Make the temperature of compsn keep below about 160 ℉.Optionally add extra MEK, climb with the inhibition mixture and mix axle.

Subsequently mixture is cooled to and is lower than about 120 ℉, and in compsn, add latent curing agent Dyhard RU 100 (Dicy) and the allophanamide (based on tolylene diamine (CA-150-Omicure U24) or CA 152-Omicure U-52-CVC Chemical) of about 1 weight % respectively.Subsequently compsn was mixed about 5-10 minute, until essentially homogenous.During solidifying agent adds, make the temperature of mixture keep below about 130 ℉.

With each compsn coarse filtration, the degassing and deposition film forming to form surface film from the preceding text compsn.EP-15 implements coarse filtration through filtration medium.Implement the degassing so that the solids content of compsn is about 80 weight %.To apply the film that becomes to have about 0.035psf film weight through the compsn of the coarse filtration and the degassing through the film coating machine subsequently, and be then dried to volatile matter less than about 1 weight %.Selected non-woven polyester or the unordered pad carrier of glass are pushed down in the film so that pad is embedded in the film at light pressure.

According to the specification sheets of prepreg manufacturers, through with surface film, laminated being incorporated in of prepreg made the composite part that adds surface film on the instrument subsequently.Subsequently, look the drafting solidification value of prepreg system and decide, composite part is being solidified about 60 minutes to 180 minutes (for example, about 90 minutes to 120 minutes) under the temperature between about 180 ℉ and 350 ℉.Setting up period under autoclave conditions is looked parts design and density of texture and is decided, and composite part is exposed under the pressure of about 14psi to 100psi about 60 minutes to 180 minutes.

Embodiment 2-comprises the conductivity measurement of the surface film of various conductive additives

To have and two-layer be cut into about 6 * 5 inches test specimen, and use four-point probe AVO

Ducter

DLRO10X numeral low resistance Ao Mubiao (Digital Low Resistivity Ohmmeter) to measure electroconductibility or surface resistivity (with ohm-sq or milliohm/square be unit) through the solidified surface film.Come surface measurements resistivity according to BMS 10-21K specification sheets (Boeing), wherein the distance between each probe is about 4 inches.

Test 1-comprises the conductivity measurement of silver-colored thin slice as the surface film of conductive additive

Use the conductive additive of silver-colored thin slice (for example from Metalor Technologies AB 0022) as the compsn of test 1.The size distribution of AB 0022 silver medal thin slice is about 13.4 μ m (D ₅₀), about 28.5 (D ₉₀) and about 64.5 (D ₁₀₀).Found conductivity meter facial mask from said composition preparation appear about 12.5 milliohms/square resistivity.

Test 2-comprises the conductivity measurement of silver-colored thin slice as the surface film of conductive additive

Use the conductive additive of silver-colored thin slice (for example EA 0295-Metalor Technologies) as the compsn of test 2.The size distribution of EA 0295 silver medal thin slice is: about 5.2 μ m (D ₅₀), about 13.34 (D ₉₀) and about 32.5 (D ₁₀₀), its size is about the half the of AB 0022 silver medal thin slice.Found conductivity meter facial mask from said composition preparation appear about 152 milliohms/square resistivity.

Test 3-comprise be coated with silver copper as the conductivity measurement of the surface film of conductive additive

Use is coated with the conductive additive of the copper (Ferro) of silver as the compsn of test 3.The copper particle that is coated with silver has the mean diameter of about 45 μ m.Found conductivity meter facial mask from said composition preparation appear about 125 to 137 milliohms/square resistivity.

Test 4-comprise be coated with silver aluminium as the conductivity measurement of the surface film of conductive additive

Use is coated with the conductive additive of the aluminium (AEE, Micron Metals company) of silver as the compsn of test 4.Found conductivity meter facial mask from said composition preparation appear 4500 milliohms/square resistivity.

Test 5-comprises the graphite that the is coated with nickel conductivity measurement as the surface modes of conductive additive

Use is coated with the conductive additive of the graphite (AEE, Micron Metals company) of nickel as the compsn of test 5.Found conductivity meter facial mask from said composition preparation appear 3100 milliohms/square resistivity.

Test 6-comprise be coated with silver nickel as the conductivity measurement of the surface film of conductive additive

Use is coated with the conductive additive of the nickel (AEE, Micron Metals company) of silver as the compsn of test 6.Found conductivity meter facial mask from said composition preparation appear less than about 6100 milliohms/square resistivity.

Test 7-comprises the conductivity measurement of carbon black as the surface film of conductive additive

Use the conductive additive of graphitized carbon black (Printex XE2-Degussa) as the compsn of test 7.The heap(ed) capacity of research between about 2.5 weight % to 7.5 weight %.Such as among Fig. 5 B displaying, found that the conductivity meter facial mask from said composition preparation presents the resistivity of about 17,000 to 47,000 ohm-sq.

Test 8-comprises the conductivity measurement of carbon nanofiber as the surface film of conductive additive

Use the conductive additive of carbon nanofiber as the compsn of test 7.The heap(ed) capacity of research between about 4 weight % to 16 weight %.Such as among Fig. 5 B displaying, found that the conductivity meter facial mask from said composition preparation presents the resistivity of about 20,000 to 200,000 ohm-sq.

The screening study general introduction

The resistivity measurement of each compsn is summarized among Fig. 6.It should be noted that with other conductive additive (for example, test 4-8) and compare,, comprise that the compsn of silver-colored thin slice additive (for example, test 1 and 2) presents low-down resistivity value for the conductive additive of identical heap(ed) capacity.These low-resistivity values and the surface film that adds the copper wire netting (about 15 milliohms/square) are quite or be superior to the latter.Said composition can be used in the surface film in order to lightning Protection.

1-6 compares with test, uses the test 7 and 8 of carbon black and carbon nanofiber to present higher relatively resistivity value.Although these additives are not suitable for the surface film in order to lightning Protection, can be used for surperficial EMI shielding and ESD and use.

Embodiment 2-silver thin slice type and heap(ed) capacity are to the influence of surface film electroconductibility

Such as among the embodiment 1 demonstration, found that the conductive additive that comprises silver-colored thin slice provides the embodiment of the surface film with low-down resistivity.For understanding of the influence of silver-colored thin slice better, the heap(ed) capacity of three kinds of silver-colored thin slice types of difference (AB 0022 and EA 0295) and silver-copper foil and electroconductibility concerned implementation system research to electrical property.These compsns such as preceding text outside the argumentation, the electroconductibility result who is obtained is summarized in the following table 3.

The type of table 3-silver thin slice and heap(ed) capacity are to the influence of the electroconductibility of surface film

Shown in table 3 and Fig. 6, along with the concentration increase of silver-colored thin slice, the resistivity of surface film significantly reduces.About 12.5 milliohms when about 4640 milliohms of resistivity when the heap(ed) capacity of about 18 weight % that for example, comprise the surface film compsn of AB 0022 silver medal thin slice are reduced to the heap(ed) capacity of about 56 weight %, about 10 milliohms during to the heap(ed) capacity of about 63 weight %.Similarly, along with the concentration of silver-colored thin slice increases to the heap(ed) capacity of 63 weight % from the heap(ed) capacity of about 56 weight %, the resistivity that comprises the surface film compsn of EA 0295 silver medal thin slice is reduced to 27 milliohms from about 152 milliohms.

In addition, find, equating under the heap(ed) capacity that it is low electroconductibility value that AB 0022 silver medal thin slice appears than EA 0295.Do not desire to be subject to theory, this observations can be explained through the size distribution and the difference in surface areas of two kinds of thin slices.AB 0022 silver medal thin slice presents bigger size distribution than EA 0295, and the charging efficiency that this tolerable is bigger helps the contact between each silver-colored thin slice.

Also can be observed, when the concentration of silver-colored thin slice AB 0022 surpassed about 40 weight %, the resistivity of compsn had obvious reduction.Such as hereinafter argumentation, we think that this result system is owing to form the interconnective stratiform network of successive basically of silver-colored thin slice.These results show that further in certain embodiments, the concentration of silver-colored thin slice can surpass about 40 weight % in the compsn.In other preferred embodiment, it is about 46% that the concentration of silver-colored thin slice can surpass, so that the surface film with resistivity level of working as with metallographic phase to be provided.

Embodiment 4-uses SEM to implement the surface film Study on Microstructure

Further inspection contains the microtexture of the composite material surface film of silver-colored thin slice (AB 0022), to understand the effect of silver-colored thin slice in the electroconductibility of surface film more fully.BoeingBMS 8-341 specification sheets according to surface film is made matrix material.For checking the microtexture of the complex layered materials of preparation in this way, sample is cut into the less size of about 10mm * 20mm, and is installed in curable epoxide (epoxicure) resin system.The Buehler Metaserv 2000 shredders/polishing machine that uses in order that reduces one by one with the abrasive size polishes checking the surface: about 320 granularities/about 1200 granularities/about 0.3 μ m aluminum oxide slurries/about 0.05 μ m aluminum oxide slurries.During the microtexture of inspection film, with platinum on the surface-coated and use Hitachi S-2700 sem (SEM) to analyze, such as among Fig. 4 displaying.

SEM inspection to this high conductivity meter facial mask has shown, forms the continuous interconnective stratiform conduction path (clear zone, Fig. 4 A) that is made up of the unordered meticulous silver-colored thin slice that is scattered in the epoxy matrix material.We think that this conductive path is the reason of uniform high conductivity basically of these conductivity meter facial masks.The bigger thin slice size (up to about 30 μ m) of silver thin slice AB 0022 and relatively large surface-area provide abundant surface-area contact, in whole matrix, to reach the successive satisfactory electrical conductivity.In matrix, sheet metal is tightly packed each other with substantially parallel orientation, and this helps electronics to pass through.

Embodiment 6-adds the surface film compsn of silver-colored thin slice and other conductive additive

Owing in containing the compsn embodiment of silver-colored thin slice, measure high conductivity, historical facts or anecdotes is executed further electroconductibility research to check silver-colored thin slice and to be used for the performance of combination of other conductive additive of further enhanced surface film composition electroconductibility.Except that novel conductive additive, the dissertator of said composition and preceding text institute no change roughly with regard to table 1.Table 4 general introduction contains the conductive additive of silver-colored thin slice and other conductive additive: independent silver-colored thin slice (baseline), silver-colored thin slice and nano silver wire, silver-colored thin slice and carbon nanotube, reach silver-colored thin slice and be coated with silver-colored glass sphere.

Table 4-contains the surface film compsn of silver-colored thin slice

Test 12-comprises silver-colored thin slice and nano silver wire (SNW) conductivity measurement as the surface film of conductive additive

Use silver-colored thin slice (AB 0022) and the conductive additive of nano silver wire (SNW-A30, SNW-A60, SNW-A300, SNW-A900-Filigree Nanotech company) as the compsn of test 9.Look selected size and the type of SNW and decide, the length of nano silver wire and diameter are that about 1 to 25 μ m and 30 is to 900nm.In addition, it is constant that the concentration of nano silver wire keeps under about 3 weight %, and the concentration of silver-colored thin slice changes between about 46 weight % to 56 weight %.Observe, the resistivity that increases compsn along with the content of silver-colored thin slice significantly reduces, about 0.2 milliohm during about 15 milliohms the during concentration of about certainly 46 weight %/square to the concentration of about 56 weight %/square.

Test 13-comprises silver-colored thin slice and the carbon nanotube conductivity measurement as the surface film of conductive additive

Use silver-colored thin slice (for example, AB 0022) and the conductive additive of carbon nanotube (CNT/ epoxy resin enriched material NP-W1M2, NP-A1M2, NP-A3M2 or NP-A2M2 are from Nanoledge) as the compsn of test 10.Look used CNT and decide, the length of CNTS and diameter can change to some extent.The concentration of silver thin slice and CNT each has variation in test 10, wherein the concentration of CNT changes between about 0.3 weight % to 1.2 weight %, and the concentration of silver-colored thin slice changes between about 51 weight % to 56 weight %.Observe, along with the content of silver-colored thin slice increases, the resistivity of compsn reduces, about 15 milliohms during about 50 milliohms the during concentration of about certainly 51 weight %/square to the concentration of about 56 weight %/square.

Test 14-comprises silver-colored thin slice and the conductivity measurement of the glass sphere that is coated with silver as the surface film of conductive additive

Use silver-colored thin slice (for example, AB 0022) and be coated with the conductive additive of the glass sphere (CNT/ epoxy resin enriched material NP-W1M2, NP-A1M2, NP-A3M2 or NP-A2M2 are from Nanoledge) of silver as the compsn of test 11.In addition, the concentration that is coated with the glass sphere of silver keeps constant under about 5 weight %, and the concentration of silver-colored thin slice changes between about 51 weight % to 56 weight %.Observe, along with the content of silver-colored thin slice increases, the resistivity of compsn reduces, about 15 milliohms during about 60 milliohms the during concentration of about certainly 51 weight %/square to the concentration of about 20 weight %/square.

Contain the general introduction of the compsn of silver-colored thin slice and other conductive additive

The resistivity measurements that in Fig. 7, compares each compsn relative to each other.On the one hand, the compsn that contains silver-colored thin slice presents the resistivity of reduction separately along with the concentration increase of silver-colored thin slice.Further comparing the performance of each compsn relative to each other, comprise that the compsn of silver-colored thin slice and nano silver wire presents optimum performance, is independent silver-colored thin slice and silver-colored thin slice and CNT (heap(ed) capacities of 1.2 weight %) secondly, and this is based on the lowest resistivity of given silver-colored thin slice heap(ed) capacity.In addition, the resistivity of this surface film compsn be no more than about 60 milliohms/square, this is still with metal

Resistivity is suitable.

Embodiment 7-lightning Protection

The electroconductibility (under the situation of not using wire netting or paper tinsel, reaching) of the higher metalloid that surface film embodiment disclosed herein is appeared makes it be applicable to lightning Protection (LSP) application.For estimating the performance that this surface film is used for the LSP of matrix material; Matrix material to adding surface film is implemented lightning test; Electrically conductive composition (for example, the compsn of the test 1) formation that this surface film is served as reasons and comprised silver-colored thin slice (heap(ed) capacity is between about 56-63 weight %).The LSP performance and the contrast of this system are compared, and this contrast comprises the same compound material and comprises the surface film that is embedded in the wire netting in the polymer compsn.

Such as preceding text argumentation, in multi-angle is laminated, use 6 to 9 layers of prepreg to make the composite material test panels, wherein the conductivity meter facial mask is as outermost layer.Subsequently with laminated and surface film in autoclave co-curing so that surface film is incorporated in the matrix material.Before lightning test, panel is further applied priming and enamel top coating.

Utilize the thunder direct effect to test and estimate the performance of composites of in the different zones of aircraft, using.According to RTCA/DO-160F, Radio Technical Commission for Aeronautics " Environmental Conditions and Test Procedures for Airborne Equipment " implements lightning test.In brief, surface film/laminated panel is fixed in correct position, and returns element with electric current and electrically contact through placing.Positioning of electrode adjoins in approximate center and with test panel.Initial lead self-electrode on specimen surface extends to initial lightning strike spot.

Implement test with the thunderbolt of emulation on the regional 2A of regional 1A of aircraft (radome) and aircraft (most of fuselage part).This test is simulated thunderbolt through making test panel stand the high testing current waveform described in the following table 5.As shown in table 5, the waveform that is applied can comprise many components, and it is looked the aircraft part of this panel plan representative and changes.

Employed waveform in the table 5-LSP test

For example, the lightning test of simulating area 1A comprises the waveform of component A, B and C with use, and the lightning test of simulating area 2A comprises use the waveform of component B, C and D.

Fig. 8 A-8B be illustrated in respectively add after the lightning test of simulating area 1A embedding the synopsis facial mask of copper mesh is arranged and contain silver-colored thin slice surface film embodiment of the present invention without the painted composite panel.Fig. 9 A-9B shows the regional 1A performance of the similar composite panel of when before test, painting, being tested.Figure 10 A-10B be illustrated in respectively add after the lightning test of simulating area 2A the surface film embodiment of the present invention that contains silver-colored thin slice through japanning and without the painted composite panel.

Usually, the surface film/laminated panel that contains silver-colored thin slice appears and has the suitable lightning Protection of performance of the contrast panel of metal copper mesh, does not have obvious break-through.In addition, surface distress is also very limited.

Through japanning and different without the viewed surface distress of painted test panel, from reticulattion burn, surperficial spottiness and upper layer layering to fiber break and do not wait.For identical surface film/matrix material structure, many usually without the painted panel through the damage that the painted panel is appeared.This difference is to reduce owing to the electric arc in the regional area in painted panel disperses the quantity in site and the dense degree of thunderbolt.

These results show that the surface film/laminated panel embodiment that contains silver-colored thin slice has important lightning Protection function, and through in regional 1A and the 2A thunder direct effect test in the two.Advantageously, this surface film/laminated panel shows and the suitable LSP of contrast panel with wire netting, and weight savings was up to about 50% when suitable LSP wherein was provided.

The test of embodiment 8-tackiness agent

Also the embodiment of this thermoset electrically conductive composition is implemented test, estimate its performance in adhesive application.The test of being implemented comprises broad area lap shear strength test and floating roller peel strength test.

Lap shear test provides the information of relevant shearing resistance when tackiness agent to by tackiness agent institute bonded adherend loading tensile the time.According to ASTM 3165, " Standard Test Method for Strength Properties of Adhesives in Shear by Tension Loading of Single-Lap-Joint Laminated Assemblies " implements broad area lap shear test under about room temperature, 180 ℉ and 250 ℉.

Floating roller peel off test provide relevant when an adherend be flexible and with the strength information of constant angle from a stiffness adhesive body release adhesive.According to ASTM D3167, " Standard Test Method for Floating Roller Peel Resistance of Adhesives " implements floating roller and peels off test under about room temperature, 225 ℉ and 250 ℉.

To testing 1 compsn implementation evaluation, said composition is used the silver-colored thin slice of the concentration of about 42 weight %.Compsn mixing mentioned above, the degassing are also applied the heat fusing film that becomes to have about 0.06psf film weight subsequently.Non-woven unordered pad carrier is pushed down in the film so that pad is bonded on the film at light pressure.With electrically conductive composition and non-woven carbon hovel or the combination of aluminium net.

Except that omitting conductive additive, use same combination to prepare control sample in a similar manner.This control sample comprises the aluminium net in addition.The test result of each tackiness agent is showed in the following table 6.

The binder performance of table 6-electrically conductive composition

Test 15-comprises silver-colored thin slice and measures as the adhesive properties of binder film on the carbon pad of conductive additive

The result of analytical table 6 can observe, and is measured as peeling off through broad area lap shear and floating roller, adhesive strength constant in the TR of being studied of the compsn of test 15.In one embodiment, in the TR that is higher than 200 ℉, about certainly room temperature is to about 250 ℉, and it is about 10% that lap shear strength only changes, between about 3000psi and 3286psi.In roughly the same TR, stripping strength changes less than 5%, between about 26pli to 27pli.

Test 16-comprises silver-colored thin slice and measures in the online adhesive properties of aluminium as the binder film of conductive additive

The result of analytical table 6 can observe, and measured as peeling off through broad area lap shear and floating roller, the adhesive strength of the compsn of test 16 shows medium variation in the TR of being studied.In one embodiment, about certainly room temperature is to about 250 ℉, and it is about 20% that lap shear strength changes, between about 3078psi to 3714psi.In roughly the same TR, stripping strength changes less than about 5pli.

Test 17-contrast binder film is measured in the online adhesive properties of aluminium

The result of analytical table 6 can observe, and measured as peeling off through broad area lap shear and floating roller, the adhesive strength of the compsn of test 17 shows medium variation in the TR of being studied.In one embodiment, about certainly room temperature is to about 250 ℉, and it is about 20% that lap shear strength changes, between about 4130psi to 4813psi.In roughly the same TR, stripping strength changes.

The test of general introduction-tackiness agent

Compare with the result of test 12-14, the electroconductive binder that contains silver-colored thin slice of test 15-16 presents good electrical conductivity (about 250 milliohms/square) and good adhesive properties (as measured through lap shear strength and stripping strength).It should be noted that adhesive properties is suitable with non-conductive contrast tackiness agent, show to use said composition under the situation of not sacrificing adhesive strength, to reach electroconductibility.This result further shows the potential suitability that this electroconductive binder is used for some aeronautics and space EME, for example the LS surface repair, as the path of return current or conductive fastener to reduce the electric capacity current potential.

Although above-mentioned explanation shows, sets forth and points out the basic novel feature that the present invention instructs; But should be appreciated that; Those skilled in the art can to apparatus shown with and uses thereof details carry out various omissions, replacement, variation and/or interpolation, this does not deviate from the scope of the present invention instruction.Therefore, the scope of the present invention's instruction should not be limited to above-mentioned argumentation, and should be defined by the claim of enclosing.

Claims

1. conductivity meter facial mask, this surface film comprises:

Thermoset polymer compositions, it comprises:

At least a thermosetting resin; And

The resistivity of wherein said surface film less than about 500 milliohms/square.

2. the surface film of claim 1, wherein thermosetting resin is selected from epoxy resin, bismaleimides, cyanate, resol, benzoxazine and functionalized polyimide.

3. the surface film of one of claim 1-2, wherein thermosetting resin exists with the concentration between about 10-60 weight %.

4. the surface film of one of claim 2-3, wherein epoxy resin comprises diglycidylether, four glycidyl ether methylene dianiline (MDA)s, the diglycidylether of tetrabromo-bisphenol and their combination of dihydroxyphenyl propane.

5. the surface film of one of claim 1-4, wherein silver-colored thin slice is taked layered struture in compsn.

6. the surface film of one of claim 1-5, wherein thermoset polymer compositions comprises the silver-colored thin slice greater than about 55 weight %, the resistivity of surface film less than 15 milliohms/square.

7. the surface film of one of claim 1-6, wherein thermoset polymer compositions comprises the silver-colored thin slice greater than about 60 weight %, the resistivity of surface film be less than or equal to 10 milliohms/square.

8. the surface film of one of claim 1-5, wherein thermoset polymer compositions further comprises nano silver wire, carbon nanotube, graphitized carbon black and is coated with at least a in the glass sphere of silver.

9. the surface film of claim 8, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 45 weight %; And

Nano silver wire;

Wherein the resistivity of surface film be less than or equal to about 15 milliohms/square.

10. the surface film of one of claim 8-9, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 50 weight %; And

Nano silver wire;

Wherein the resistivity of surface film be less than or equal to about 5 milliohms/square.

11. the surface film of one of claim 8-10, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 55 weight %; And

Nano silver wire;

Wherein the resistivity of surface film be less than or equal to about 0.2 milliohm/square.

12. the surface film of one of claim 9-11, wherein the concentration of nano silver wire is about 3 weight %.

13. the surface film of claim 8, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 50 weight %; And

Carbon nanotube greater than about 0.3 weight %;

Wherein the resistivity of surface film be less than or equal to about 50 milliohms/square.

14. the surface film of claim 8, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 50 weight %; And

Carbon black greater than about 3 weight %;

Wherein the resistivity of surface film be less than or equal to about 70 milliohms/square.

15. the surface film of claim 8, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 50 weight %; And

Be coated with the glass sphere of silver;

Wherein the resistivity of surface film be less than or equal to about 60 milliohms/square.

16. the said surface film of claim 15, the concentration that wherein is coated with the glass sphere of silver is about 5 weight %.

17. a conductivity meter facial mask, this surface film comprises:

Thermoset polymer compositions, it comprises:

At least a thermosetting resin; And

The graphitized carbon black of about 2-8 weight %;

Wherein the resistivity of surface film is less than about 50 ohm-sq.

18. a matrix material, it comprises the surface film of one of claim 1-17.

19. an electrically conductive composition, it comprises:

One or more thermosetting resins of about 10-60 weight %;

One or more solidifying agent of about 0.5-30 weight %; And

One or more conductive additives of about 2-70 weight %;

Wherein the concentration gross weight that is based on compsn is measured;

Wherein select the concentration of conductive additive, this electrically conductive composition is appeared between about 1 * 10 ^-6Ohm-sq to 1 * 10 ⁸Resistivity between the ohm-sq.

20. the electrically conductive composition of claim 19, wherein thermosetting resin is selected from epoxy resin, bismaleimides, cyanate, resol, benzoxazine and functionalized polyimide.

21. the electrically conductive composition of one of claim 19-20, wherein thermosetting resin exists with the concentration between about 10-60 weight %.

22. the electrically conductive composition of one of claim 20-21; Wherein thermosetting resin comprises diglycidylether, four glycidyl ether methylene dianiline (MDA)s, the diglycidylether of tetrabromo-bisphenol, 4-glycidyl oxygen base--the N of dihydroxyphenyl propane, N '-2-glycidyl aniline and their combination.

23. the electrically conductive composition of one of claim 19-22, wherein solidifying agent be selected from Dyhard RU 100, allophanamide, 4,4 '-diamino diphenyl sulfone (4,4 '-DDS) and boron trifluoride.

24. the electrically conductive composition of one of claim 19-23, wherein conductive additive comprise silver-colored thin slice, silver powder, be coated with silver copper foil, be coated with silver aluminum slice, be coated with nickel, the graphite that is coated with nickel, graphitized carbon black, the carbon nanofiber of silver and be coated with the carbon nanofiber of metal.

25. the electrically conductive composition of claim 24, wherein conductive additive comprises the copper particle that is coated with silver greater than about 50 weight %, and the resistivity of compsn is less than about 5 ohm-sq.

26. the electrically conductive composition of claim 24, wherein conductive additive comprises the al particulate that is coated with silver greater than about 50 weight %, and the resistivity of compsn is less than about 5 ohm-sq.

27. the electrically conductive composition of claim 24, wherein conductive additive comprises the nickel particle that is coated with silver greater than about 50 weight %, and the resistivity of compsn is less than about 6.5 ohm-sq.

28. the electrically conductive composition of claim 24, wherein conductive additive comprises the graphite that is coated with nickel greater than about 50 weight %, and the resistivity of compsn is less than about 3.5 ohm-sq.

29. the electrically conductive composition of claim 24, wherein conductive additive comprises the carbon black greater than about 2 weight %, and the resistivity of compsn is less than about 50 ohm-sq.

30. the electrically conductive composition of claim 24, wherein conductive additive comprises the carbon nanofiber greater than about 4 weight %, and the resistivity of compsn is less than about 200 ohm-sq.

31. the electrically conductive composition of claim 24, wherein silver-colored thin slice is taked layered struture in said composition.

32. the electrically conductive composition of claim 31, wherein thermoset polymer compositions comprises the silver-colored thin slice greater than about 45 weight %, the resistivity of compsn less than 500 milliohms/square.

33. the electrically conductive composition of one of claim 31-32, wherein thermoset polymer compositions comprises the silver-colored thin slice greater than about 55 weight %, the resistivity of compsn less than 15 milliohms/square.

34. the electrically conductive composition of one of claim 31-33, wherein thermoset polymer compositions comprises the silver-colored thin slice greater than about 60 weight %, the resistivity of compsn be less than or equal to 10 milliohms/square.

35. the electrically conductive composition of claim 24, it further comprises:

Silver-colored thin slice greater than about 45 weight %; And

Nano silver wire;

Wherein the resistivity of compsn be less than or equal to about 15 milliohms/square.

36. the electrically conductive composition of claim 24, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 50 weight %; And

Nano silver wire;

Wherein the resistivity of compsn be less than or equal to about 5 milliohms/square.

37. the electrically conductive composition of claim 24, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 55 weight %; And

Nano silver wire;

Wherein the resistivity of compsn be less than or equal to about 0.2 milliohm/square.

38. the electrically conductive composition of one of claim 35-37, wherein the concentration of nano silver wire is about 3 weight %.

39. the electrically conductive composition of claim 24, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 50 weight %; And

Carbon nanotube greater than about 0.3 weight %;

Wherein the resistivity of compsn be less than or equal to about 50 milliohms/square.

40. the electrically conductive composition of claim 24, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 50 weight %; And

Be coated with the glass sphere of silver;

Wherein the resistivity of compsn be less than or equal to about 60 milliohms/square.

41. the electrically conductive composition of claim 40, the concentration that wherein is coated with the glass sphere of silver is about 5 weight %.

42. the electrically conductive composition of claim 24, wherein thermoset polymer compositions comprises:

Silver-colored thin slice greater than about 50 weight %; And

Carbon black greater than about 3 weight %;

Wherein the resistivity of compsn be less than or equal to about 70 milliohms/square.

43. a surface film, it comprises the compsn of one of claim 19 to 42.

44. a matrix material, it comprises the surface film of claim 43.

45. an electrically conductive adhesive film, it comprises the compsn of one of claim 19 to 42.

46. the electrically conductive adhesive film of claim 45, wherein the lap shear strength scope according to the measured tackiness agent of ASTM 3165 is greater than about 3000psi.

47. the electrically conductive adhesive film of claim 45, wherein the stripping strength scope according to the measured tackiness agent of ASTM 3167 is greater than about 25pli.

48. a method that forms the conductivity meter face mould, it comprises:

The electrically conductive composition of one of claim 19 to 42 is provided; And

This electrically conductive composition is applied to carrier.

49. the method for claim 48, wherein carrier comprises wire netting, tinsel, non-woven mat, unordered pad, knitting carrier, is coated with the carbon hovel of metal.

50. the method for one of claim 48 to 49, wherein the aerial density of electrically conductive composition is about 0.01-0.15psf (50 to 750gsm).

51. a method that forms matrix material, it comprises the surface film of claim 43 and composite prepreg co-curing.

52. a method that forms matrix material, its surface film that comprises claim 43 is bonded to matrix material.

53. the method for claim 52, it further is included under the temperature between about 160 to 360 ℉ and makes surface film be bonded to matrix material.